This article reports the designed preparation of two different kinds of novel porous metal nanostructured films, namely, an ordered macroporous Au/Ag nanostructured film and an ordered hollow Au/Ag nanostructured film. Different from previous reports, the presently proposed method can be conveniently used to control film structures by simply varying the experimental conditions. The morphology of these films has been characterized by scanning electron microscopy (SEM), and their performance as surface-enhanced Raman scattering (SERS) substrates has been evaluated by using rhodamine 6G (R6G) as a probe molecule. We show that such porous nanostructured films consisting of larger interconnected aggregates are highly desirable as SERS substrates in terms of high Raman intensity enhancement, excellent stability, and reproducibility. The interconnected nanostructured aggregate, long-range ordering porosity, and nanoscale roughness are important factors responsible for this large SERS enhancement ability.